Significant Promotional Effect of Nb Doping in Bifunctional Pd/WOx Nanocatalysts on One‐Step Benzene Hydroalkylation

The development of high‐efficiency bifunctional metal‐acid catalysts with an appropriate metal‐acid balance for the production of cyclohexylbenzene (CHB) via the one‐step tandem benzene hydroalkylation still faces a dilemma because of the difficulty in inhibiting the over hydrogenation of benzene substrate and cyclohexene intermediate and controlling target product selectivity. In this study, Nb‐doped WOx supported Pd nanocatalysts were developed. It has shown that doping Nb into WOx supports altered surface properties and microstructures of catalysts, resulting in the generation of more surface acidic sites and defective W‐Ov‐Nb structures (Ov: oxygen vacancies). As‐constructed Pd‐based nanocatalyst with only 0.1 wt% Pd loading and a Nb/(Nb+W) molar ratio of 0.25 exhibited superior catalytic benzene hydroalkylation performance to undoped supported Pd catalyst, with a much higher yield of CHB (35.6%) at 220 °C. It was authenticated that highly dispersed Pd sites facilitated the dissociation of hydrogen molecules, defective W‐Ov‐Nb structures were conductive to the surface transfer of active hydrogen species, abundant acidic sites favored benzene/cyclohexene adsorption, and abundant Brønsted acidic sites promoted the alkylation between cyclohexene formed and benzene. Accordingly, excellent cooperative catalysis between Pd sites, acidic sites, and oxygen vacancies contributed to improved catalytic performance of Nb‐doped WOx supported Pd catalysts in benzene hydroalkylation.